I need to connect to a webservice which is behind of a VPN
via PHP. My server is Debian Linux (Squeeze).
From PHP point of view, the VPN is just a plain network connection. It does not require additional handling.
If you want to dynamicaly estabilish a VPN connection, you'll probably need to use exec() and some commandline tool for estabilishing a connection. But as such connection doesn't interfere with normal network communication (as long as it's properly configured, with other subnet ip range), you should estabilish it once and keep it active for PHP and other apps to use.